CN103318978B - Preparation method of mesoporous nickel cobaltate fiber and application thereof - Google Patents
Preparation method of mesoporous nickel cobaltate fiber and application thereof Download PDFInfo
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Abstract
The invention brings forward a preparation method of mesoporous nickel cobaltate fiber. According to the preparation method, an organic solvent is added during the preparation process of a precursor; a mixed phase of a water phase and an organic phase is used as a solvent, soluble nickel salt and cobalt salt are used as raw materials, and oxalate is used as a precipitating agent; in a system of Ni<2+>-Co<2+>-NH3-NH4<+>-SG<n->-C2O4<2->-H20-C2H5OH, a fibrous precursor is prepared; and the fibrous precursor is subjected to thermal decomposition in the air atmosphere at 250-400 DEG C so as to obtain the mesoporous NiCo2O4 fiber. According to the invention, coprecipitation based on the Ni-Co ratio set in the raw materials is effectively realized. The prepared NiCo2O4 powder is a cubic phase, has high purity and large specific surface area, is fibrous and porous, and is applicable to be used as a catalyst or an alkaline solution oxygen-evolution/hydrogen-evolution electrode material or direct alcohol fuel cell anode catalyst. The method provided by the invention is simple to operate and easy to control, has advantages of mild condition and low cost, and is suitable for commercialized production.
Description
Technical field
The invention belongs to one dimension transition metal oxide field, be specifically related to preparation method and the application thereof of a kind of cobalt acid nickel.
Background technology
In recent years, direct alcohol fuel cell is because of its nontoxicity, theoretical energy density advantages of higher and obtain extensive concern.Currently used anode catalyst mostly is the precious metal such as platinum, ruthenium and binary thereof or multicomponent material, cost is high, in cell reaction, easy CO is poisoning, therefore find and there is the base metal anode catalyst as an alternative of good catalytic and low cost, become direct alcohol fuel cell development in the urgent need to.Cobalt acid nickel (NiCo
2o
4) be a kind of composite oxides with inverse spinel structure, having excellent chemical property, higher than single metallic nickel, cobalt/cobalt oxide, there is Co in its electroconductibility and electrochemical activity
3+/ Co
2+and Ni
3+/ Ni
2+redox couple, is widely applied in catalytic field, electrochemical industry, field of environment protection.Such as: in catalyst application, owing to having the NiCo of spinel structure
2o
4active high, good stability, is used as the active ingredient of administering Organic Waste Gas Pollution used catalyst, can replaces the precious metals such as expensive platinum, rhodium, palladium; In electrode materials, NiCo
2o
4be a kind of desirable anode of electrolytic water material, to the precipitation of oxygen and reduction, all there is good catalytic performance; As electrode material for super capacitor, cobalt acid nickel has higher ratio capacitance, alternative RuO
2; In addition, due to the electrocatalysis characteristic that it is good, cobalt acid nickel can also as anode material of lithium-ion battery, high multiplying power lithium ion anode material etc.Although the purposes of cobalt acid nickel is so extensive, up to the present, people are also little to the applied research of cobalt acid nickel in direct alcohol fuel cell.In addition, performance and the material geometrical morphology of material have direct relation, and one dimension porous nanometer material is owing to having good contact, and short electronics and ion transport path and high specific conductivity, can effectively improve its electrocatalysis characteristic, become the study hotspot of people.
The primary synthetic methods of cobalt acid nickel has: high temperature solid-state method, mechanochemical synthesis, sol-gel method, liquid phase chemical co-precipitation, spray-wall interaction, hydrothermal method etc.But due to its heat-labile character, between 400 ~ 600 DEG C can decomposed become a simple oxide and another be rich in the Spinel of cobalt, make some active as catalytic activity reduces, therefore, conventional high temperature solid-state method is to the sour nickel of cobalt and be not suitable for.A large amount of strain and defect is introduced, product bad dispersibility in Mechano-chemical Synthesizing process; Powder diameter prepared by spray heating decomposition is comparatively large, and easily solute segregation occurs; Sol-gel method is by adding tensio-active agent, and the grain diameter of product is little, distributed components, but cost is higher, easily introduces impurity.Hydrothermal method needs higher temperature and pressure, requires higher, be difficult to industrialization expanding production to reaction conditions and equipment material.By contrast, co-precipitation thermal decomposition method has that powder morphology is controlled, stoichiometry accurately, be easy to the advantages such as suitability for industrialized production, be the method for current most study.But because the solubleness of different metal compound is different with precipitation kinetics, traditional coprecipitation method is easy to segregation occurs, cause coprecipitation process to be actually the fractional precipitation of each component, namely coprecipitated product belongs to mechanical mixture on microcosmic, have impact on NiCo
2o
4the physicals of powder and chemical property.Therefore, research and development one can effectively realize metal ion co-precipitation, and morphology controllable, cost are lower, and product physicochemical property is excellent, are realize suitability for industrialized production high-performance NiCo
2o
4the effective way of powder.The people such as JiangHao (Hao Jiang et al.Hierarchical porous NiCo
2o
4nanowires forhigh-rate supercapacitors.Chem.Comm., 2012,48,4465-4467) adopt oxalic acid to be precipitation agent, Ni (NO
3) 6H
2o and Co (NO
3) 6H
2o is raw material, P123 is soft template, ethanol and PEG are solvent, adopt co-precipitation thermal decomposition method to synthesize and have classifying porous cobalt acid nickel fiber, and have studied its application as high magnification electrical condenser aspect, the method take P123 as soft template, in production process, processing condition are restive, in addition, due in a large number with an organic solvent, cause cost compare high.Chinese patent (CN201110195864.X, 2011) provides a kind of coprecipitation method of nickel cobaltate nano particles, respectively by precipitation agent sodium hydroxide and nickel cobalt metal nitrate Ni (NO
3) 6H
2o and Co (NO
3) 6H
2o is dissolved in ethylene glycol or dimethyl formyl ammonium organic solvent, metal salt solution is joined in precipitant solution, under 0-80 DEG C of conditions, stir 0.5-48 hours, presoma can be obtained, then presoma is obtained nano nickel cobalt oxide material 300-400 DEG C of thermolysis, make capacitor electrode material with this material, its ratio capacitance can reach 671Fg
-1.The method is simple to operate, mild condition, but organic reagent used is ethylene glycol or dimethylformamide, and is 1 ~ 10:1 with the ratio of deionized water, and cost compare is high, and in addition, owing to adding sodium hydroxide, specific filtration resistance is more difficult, industrial operation difficulty.Patent (CN03159576,2003) has invented a kind of preparation method preparing fibrous nickel cobalt composite oxide powder, at Ni
2+-Co
2+-NH
3-NH
4+-SG
n--C
2o
4 2--H
2in O reaction system, adopt and coordinate co-precipitation thermal decomposition method, under 600 DEG C of-900 DEG C of conditions, prepared fibrous nickel cobalt composite oxide powder.The method is in precursor synthesis process, its pH controls in the weakly alkaline environment of 7.0-9.0, the nickel cobalt ion nickel cobalt proportioning be difficult to set in raw material enters in co-precipitation common property thing, and experimentation needs accurately to control, and realizes poor reproducibility, industrial application difficulty, heat decomposition temperature are high, energy consumption is large, and product purity is low, is generally the mixture of nickel oxide, cobalt oxide, nickel/cobalt composite oxide, specific surface area is little, and catalytic activity is low.The applicant once Ph D dissertation (profound cyanines. fibrous porous superfine special nickel cobalt (alloy) and composite oxide power novel preparation method research, Ph.D. Dissertation, Central South University, 2006) a kind of preparation method preparing fibrous nickel cobalt-base alloy and composite oxides powder of cobalt nicker end is disclosed, at Ni
2+-Co
2+-NH
3-NH
4+-Cl
--C
2o
4 2--H
2in O-A reaction system, adopt and coordinate co-precipitation thermal decomposition method, in oxygen atmosphere, prepared fibrous porous composite oxides powder of cobalt nicker end.The method is in oxygen atmosphere, and presoma needs just can obtain fibrous porous cobalt acid nickel heat decomposition temperature about 500 DEG C, and according to the character of cobalt acid nickel itself, this kind of cobalt acid nickel powder purity is low, and specific surface area is little, and catalytic activity is low, and energy consumption is high.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, propose a kind of preparation method of mesoporous cobalt acid nickel fiber.Described mesoporous NiCo
2o
4the preparation method of fiber is that oxalate is precipitation agent, and ammonia is pH value regulator, and ethanol and deionized water are solvent, at Ni with soluble nickel salt and cobalt salt for raw material
2+-Co
2+-NH
3-NH
4 +-SG
n--C
2o
4 2--H
2o-C
2h
5oH (SG
n-represent acid group Cl
-, SO
4 2-, NO
3-or CH
3cOO
-) obtaining precursor solution in system, presoma obtains mesoporous cobalt acid nickel fiber through washing, dry and thermolysis.
Another object of the present invention is the mesoporous cobalt acid nickel fiber that this preparation method of proposition obtains.
3rd object of the present invention proposes the application of mesoporous cobalt acid nickel fiber as alcohol fuel battery electrode materials.
The technical scheme realizing above-mentioned purpose of the present invention is:
A preparation method for mesoporous cobalt acid nickel fiber, comprises step:
1) soluble nickel salt and solubility cobaltates are dissolved in deionized water, are configured to containing Ni
2+/ Co
2+mol ratio is the mixed salt solution A of 1:2;
2) oxalate is stoichiometrically dissolved in the mixed solvent of organic reagent and deionized water, is configured to oxalate solution B;
3) the mixed salt solution A that step 1) configures is joined step 2) in the oxalate solution B that configures, control temperature of reaction is 50 ~ 75 DEG C simultaneously, with ammoniacal liquor regulator solution pH to 7.5 ~ 8.6, dropwise and continue to stir 0-2 hour, obtain precursor solution;
4) by step 3) precursor solution that obtains filters, with deionized water and absolute ethanol washing, the presoma after washing is dry;
5) by step 4) at obtained dried presoma is placed in temperature 250 ~ 400 DEG C, carries out thermolysis 0.5 ~ 5 hour in air atmosphere, after cooling, obtain mesoporous NiCo
2o
4fiber.
In step 3), when solution A joins in oxalate solution B, need fully dispersion, can stir on dropping limit, limit.
In step 4), available deionized water wash 3-5 time, then uses absolute ethanol washing 2-3 time.Described drying can adopt and be placed in vacuum drying oven or air dry oven, dry 10-48 hour at 70-150 DEG C; Also the additive method of this area routine can be adopted, such as seasoning, except anhydrating and dehydrated alcohol.
Wherein, described soluble nickel salt is selected from the one in six water nickelous chlorides, seven water single nickel salts, six water nickelous nitrates, nickelous chloride, single nickel salt, nickelous nitrate; Described soluble cobalt is selected from the one in cobalt chloride, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, CoCL2 6H2O, heptahydrate, cobalt nitrate hexahydrate.
Wherein, in described mixed salt solution A, Ni
2+and Co
2+total concn be 0.3mol/L ~ 1.2mol/L.
Wherein, described organic reagent is the ethanol that purity is greater than 99.0%; Described step 3) in precursor solution in, the volume ratio of organic reagent and deionized water is 1:1-20.
Preferably, in described precursor solution, the volume ratio of organic reagent and deionized water is 1:1-9.
Wherein, described oxalate is oxalic acid or ammonium oxalate, and the concentration of oxalate is 0.3mol/L ~ 1.8mol/L.
Wherein, the Ni in described step 3) Oxalate and described mixed salt solution A
2+and Co
2+the ratio of total amount of substance be 1:1.0 ~ 1.5.
The mesoporous cobalt acid nickel fiber that method of the present invention prepares.
The application in direct alcohol fuel cell electrode materials prepared by mesoporous cobalt acid nickel fiber of the present invention.Described application is with the fiber-modified glass-carbon electrode of mesoporous cobalt acid nickel.
Preferably, described direct alcohol fuel cell is preferably Direct Ethanol Fuel Cell, and described electrode materials is anode electrode material.The method of embody rule is: mesoporous cobalt acid nickel is scattered in water, is coated in glassy carbon electrode surface, and then applies Nafion solution, dry obtained anode electrode material.Active substance charge capacity 0.1-1mg/cm on the glass-carbon electrode that mesoporous cobalt acid nickel is modified
2.
Beneficial effect of the present invention is:
1. the present invention adopts co-precipitation thermal decomposition method, at normal temperatures and pressures at Ni
2+-Co
2+-NH
3-NH
4 +-SG
n--C
2o
4 2--H
2o-C
2h
5oH (SG
n-represent acid group Cl
-, SO
4 2-, NO
3 -or CH
3cOO
-) effectively achieve in raw material the co-precipitation setting nickel cobalt proportioning in system, define fibrous presoma, mesoporous cobalt acid nickel fiber can be obtained in 250-400 DEG C of air atmosphere; Whole preparation process is simple to operate, environmental friendliness, and experiment circulation ratio is very good, and cost is low, be easy to suitability for industrialized production.
2. mesoporous NiCo prepared by the method that the present invention proposes
2o
4fiber, purity is high, and specific surface area is large, is applicable to electrochemical catalysis.The result of electro-chemical test shows, the fiber-modified glass-carbon electrode of mesoporous cobalt acid nickel has good catalytic performance, and has long-term cyclical stability.
3. gained mesoporous cobalt acid nickel fiber is spinel type Emission in Cubic, purity is high, have higher specific surface area, can be used as Direct Ethanol Fuel Cell anode catalyst, the ethanol of 5mmol/L can be greater than by catalytic level, also be suitable in basic solution and analyse oxygen, hydrogen evolution electrode material, electrode material for super capacitor.
Accompanying drawing explanation
Fig. 1 is mesoporous NiCo prepared by embodiment 1
2o
4the SEM figure of Precursors of Fibers
Fig. 3 is the SEM figure of mesoporous cobalt acid nickel fiber prepared by embodiment 1
Fig. 2 is mesoporous cobalt acid nickel Co prepared by embodiment 1
2o
4the XRD figure spectrum of fiber;
Fig. 4 is the nitrogen adsorption-desorption isothermal curve of mesoporous cobalt acid nickel fiber.
Fig. 5 is the pore size distribution curve of obtained mesoporous cobalt acid nickel fiber.
Fig. 6 is the cyclic voltammetry curve of platinum carbon dioxide process carbon electrode under different ethanol concentration that fibrous cobalt acid nickel is modified.
Fig. 7 be porous cobalt acid nickel modify glass-carbon electrode and blank glass-carbon electrode scheming with or without the CV in ethanolic soln.
Fig. 8 is the cycle life figure (electrolyte solution is 1MNaOH solution) of fibrous cobalt acid nickel
Embodiment
Now with following most preferred embodiment, the present invention is described, but is not used for limiting the scope of the invention.
Embodiment 1:
1) weighing 0.02mol purity is respectively the NiCl of 98.0%
26H
2o and 0.04mol purity is 99.0%CoCl
26H
2o, NiCl
26H
2o and CoCl
26H
2the ratio of O amount is 1:2.By NiCl
26H
2o and CoC
l26H
2o is dissolved in 100ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A100ml, in this mixed salt solution A, Ni
2+and Co
2+total concn is 0.6mol/L.
2) by 0.072mol purity be 99% oxalic acid be dissolved in the mixed solvent of 50ml organic reagent ethanol and 50ml deionized water, described organic reagent to be purity be 99.7% ethanol, be configured to oxalic acid solution B.
3) 100ml mixed salt solution A step 1 configured is added drop-wise in the oxalic acid solution B that 100ml step 2 configures, and dropping limit, limit is stirred, and control temperature of reaction is 60 DEG C simultaneously, use ammoniacal liquor adjust ph, keep pH value to be 8.2, dropwise and continue stirring 0.5 hour, obtain precursor solution;
4) by step 3) precursor solution that obtains filters, and with deionized water wash four times, with absolute ethanol washing twice, obtained presoma, is placed on vacuum drying oven by this presoma, under temperature 100 DEG C of conditions dry 24 hours; Dried presoma SEM photo is as Fig. 1.
5) by step 4) obtained dried presoma is placed in the electric furnace that PID regulates, and control temperature is 300 DEG C, carries out thermolysis in air atmosphere 1 hour, and cooling, obtains mesoporous NiCo
2o
4fiber.Its SEM photo is as Fig. 2.
6) by step 5) the mesoporous cobalt acid nickel fiber that obtains characterizes, the position of the X ray diffracting data of XRD figure spectrum corresponding to (Fig. 3) and diffraction peak and Spinel NiCo
2o
4standard card (JCPDS No.20-0781) consistent, do not occur other impurity phases, what show to synthesize is cobalt acid nickel, and purity is high.From the nitrogen adsorption-desorption isothermal curve result of Fig. 4, the mesoporous cobalt acid nickel fiber of synthesis has higher specific surface area (54.5m
2g
-1), the pore size distribution curve of Fig. 5 shows that the hole of cobalt acid nickel powder is mesoporous (mean pore size is 13.4nm), the larger (76.8m of desorption pore specific surface area
2g
-1).
Embodiment 2: electrode materials prepared by mesoporous cobalt acid nickel and electrochemical Characterization thereof
Use the glass-carbon electrode modified as working electrode.First on polishing cloth, glass-carbon electrode is ground, to smooth surface with the aluminum oxide polishing powder of 50nm; After supersound washing three times in distilled water, dry rear stand-by.Get mesoporous cobalt acid nickel by powder 0.05g prepared by step embodiment 1, be dissolved in 2mL distilled water, ultrasonic disperse is even; Draw 0.4 μ L sample with microsyringe, be coated in glassy carbon electrode surface.After drying at normal temperatures, the Nafion solution (0.5wt%) getting 0.2 μ L is coated in sample surfaces.Under normal temperature after drying, namely obtain the glass-carbon electrode that mesoporous cobalt acid nickel is modified, charge capacity is 0.5mg/cm
2.
The glass-carbon electrode that mesoporous cobalt acid nickel is modified is placed in containing ethanol and NaOH solution, using platinized platinum (1cm × 1cm) as to electrode, 232 type saturated calomel electrode (SCE) are as reference electrode, electro-chemical test (Fig. 6 is carried out to the platinum carbon dioxide process carbon electrode that cobalt acid nickel is modified, cyclic voltammetry curve, sweep velocity 50mV/s).In Fig. 6, the alcohol concn that each sequence number represents is respectively 1:0.5M, 2:0.2M, 3:0.1M, 4:0.05M, 5:0.02M, 6:0.005M, 7:0M.During to alcohol catalysis, ethanol Cmin only has 0.005mol/L, embodies good electrical catalytic performance.
The glass-carbon electrode modified not have mesoporous cobalt acid nickel, for working electrode, does electro-chemical test (cyclic voltammetric) equally, and the results contrast of the glass-carbon electrode modified with mesoporous cobalt acid nickel is shown in Fig. 7.In Fig. 7, each sequence number represents 1: cobalt acid nickel modified glassy carbon electrode is at ethanolic soln (the concentration 0.5M of ethanol, electrolyte solution is 1MNaOH solution) in CV curve, 2: cobalt acid nickel modified glassy carbon electrode is without the CV curve in ethanolic soln, 3: blank glass-carbon electrode is CV curve in ethanolic soln, 4: blank glass-carbon electrode is without the CV curve in ethanolic soln.As shown in Figure 7, mesoporous cobalt acid nickel has good catalytic performance.
As Fig. 8.Mesoporous cobalt acid nickel modified glassy carbon electrode carries out 500 circulations in 0.5M ethanolic soln (electrolyte solution is 1MNaOH solution), the relatively curve (2-500th cycle) of the 1st circulation (1-1st cycle) and the 500th circulation, result shows through 500 redox circulations, peak current only have dropped 25%, has good cyclical stability.
Embodiment 3:
1) weighing 0.02mol purity is respectively the NiCl of 98.0%
26H
2o and 0.04mol purity is 99.0%CoCl
26H
2o, described NiCl
26H
2o and CoCl
26H
2the ratio of O amount is 1:2.By described NiCl
26H
2o and CoCl
26H
2o, is jointly dissolved in 100ml deionized water, is mixed with containing Ni
2+and Co
2+mixed salt solution A100ml, in described mixed salt solution A, Ni
2+and Co
2+total concn is 0.6mol/L.
2) by 0.072mol purity be 99.0% ammonium oxalate be dissolved in the mixed solvent of 20ml ethanol and 80ml deionized water, this ethanol to be purity be 99.7% ethanol, be configured to oxalate solution B.
3) 100ml mixed salt solution A step 1 configured is added drop-wise to 100ml step 2) in the oxalic acid solution B that configures, dropping limit, limit is stirred, and control temperature of reaction is 60 DEG C simultaneously, use ammoniacal liquor adjust ph, keep pH value to be 8.0, dropwise and continue stirring 0.5 hour, obtain precursor solution;
4) by step 3) the described precursor solution that obtains filters, and with deionized water wash 5 times, with absolute ethanol washing 2 times, obtained presoma, is placed on vacuum drying oven inner drying 24 hours by this presoma;
5) by step 4) presoma of obtained drying is placed in the electric furnace that PID regulates, and control temperature is 280 DEG C, carries out thermolysis in air atmosphere 2 hours, obtains mesoporous NiCo
2o
4fiber.
By step 5) the mesoporous cobalt acid nickel fiber that obtains characterizes, the bright synthesis of XRD figure stave be the sour nickel of cobalt, purity is high, does not have impurity.Tested from nitrogen adsorption-desorption isothermal curve, the mesoporous cobalt acid nickel fiber of synthesis has 53.9m
2g
-1specific surface area.
Embodiment 4:
1) weighing 0.02mol purity is respectively the NiCl of 98.0%
26H
2o and 0.04mol purity is 99.0%CoCl
26H
2o, NiCl
26H
2o and CoCl
26H
2the ratio of O amount is 1:2.By NiCl
26H
2o and CoCl
26H
2o is dissolved in 100ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A100ml, in this mixed salt solution A, Ni
2+and Co
2+total concn is 0.6mol/L.
2) by 0.072mol purity be 99.0% oxalic acid be dissolved in the mixed solvent of 90ml organic reagent ethanol (purity is 99.7%) and 10ml deionized water, be configured to oxalic acid solution B.
3) 100ml mixed salt solution A step 1 configured is added drop-wise in the oxalic acid solution B that 100ml step 2 configures, and dropping limit, limit is stirred, and control temperature of reaction is 60 DEG C simultaneously, use ammoniacal liquor adjust ph, keep pH value to be 8.6, dropwise and continue stirring 0.5 hour, obtain precursor solution;
4) by step 3) precursor solution that obtains filters, and with deionized water wash 4 times, with absolute ethanol washing 3 times, obtained presoma, is placed on vacuum drying oven dry 24 hours by this presoma;
5) by step 4) presoma of obtained drying is placed in the electric furnace that PID regulates, and control temperature is 400 DEG C, carries out thermolysis in air atmosphere 1 hour, obtains mesoporous NiCo
2o
4fiber.
By step 5) the mesoporous cobalt acid nickel fiber that obtains characterizes, the bright synthesis of XRD figure stave be the sour nickel of cobalt, purity is high, does not have impurity.Tested from nitrogen adsorption-desorption isothermal curve, the mesoporous cobalt acid nickel fiber of synthesis has 55.2m
2g
-1specific surface area.
Embodiment 5:
1) weighing 0.01mol purity is respectively the Ni(NO of 98.0%
3)
26H
2o and 0.02mol purity is 99.0%Co(NO
3)
26H
2o, Ni(NO
3)
26H
2o and Co(NO
3)
26H
2the ratio of O amount is 1:2.By Ni(NO
3)
26H
2o and Co(NO
3)
26H
2o is dissolved in 100ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A100ml, in described mixed salt solution A, Ni
2+and Co
2+total concn is 0.3mol/L.
2) by 0.045mol purity be 99.0% ammonium oxalate be dissolved in the mixed solvent of 50ml organic reagent ethanol and 50ml deionized water, described organic reagent to be purity be 99.7% ethanol, be configured to oxalic acid solution B.
3) 100ml mixed salt solution A step 1 configured is added drop-wise in the oxalic acid solution B that 100ml step 2 configures, and dropping limit, limit is stirred, and control temperature of reaction is 60 DEG C simultaneously, use aqueous ammonia conditions pH value, keep pH value to be 8.2, dropwise and continue stirring 0.5 hour, obtain precursor solution;
4) by step 3) the described precursor solution that obtains filters, and with deionized water wash four times, with absolute ethanol washing twice, obtained presoma, is placed on vacuum drying oven dry 24 hours by this presoma;
5) by step 4) the described presoma of obtained drying is placed in the electric furnace that PID regulates, and control temperature is 280 DEG C, carries out thermolysis in air atmosphere 1 hour, obtains mesoporous NiCo
2o
4fiber.
By step 5) the mesoporous cobalt acid nickel fiber that obtains characterizes, the bright synthesis of XRD figure stave be the sour nickel of cobalt, purity is high, does not have impurity.Tested from nitrogen adsorption-desorption isothermal curve, the mesoporous cobalt acid nickel fiber of synthesis has 55.8m
2g
-1specific surface area.
Embodiment 6:
1) weighing 0.04mol purity is respectively the NiSO of 98.0%
47H
2o and 0.08mol purity is 99.0%CoSO
47H
2o, NiSO
47H
2o and CoSO
47H
2the ratio of O amount is 1:2.By NiSO
47H
2o and CoSO
47H
2o is dissolved in 100ml deionized water jointly, is mixed with containing Ni
2+and Co
2+mixed salt solution A100ml, in described mixed salt solution A, Ni
2+and Co
2+total concn is 1.2mol/L.
2) by 0.18mol purity be 99.0% ammonium oxalate be dissolved in the mixed solvent of 50ml organic reagent ethanol and 10ml deionized water, described organic reagent to be purity be 99.7% ethanol, be configured to oxalate solution B.
3) 100ml mixed salt solution A step 1 configured is added drop-wise to 100ml step 2) in the oxalate solution B that configures, dropping limit, limit is stirred, and control temperature of reaction is 65 DEG C simultaneously, use ammoniacal liquor adjust ph, keep pH value to be 8.2, dropwise and continue stirring 0.5 hour, obtain precursor solution;
4) by step 3) the described precursor solution that obtains filters, and with deionized water wash four times, with absolute ethanol washing twice, obtained presoma, is placed on vacuum drying oven dry 24 hours by this presoma;
5) by step 4) the described presoma of obtained drying is placed in the electric furnace that PID regulates, and control temperature is 350 DEG C, carries out thermolysis in air atmosphere 1 hour, obtains mesoporous NiCo
2o
4fiber.
By step 5) the mesoporous cobalt acid nickel fiber that obtains characterizes, the bright synthesis of XRD figure stave be the sour nickel of cobalt, purity is high, does not have impurity.Tested from nitrogen adsorption-desorption isothermal curve, the mesoporous cobalt acid nickel fiber of synthesis has 54.9m
2g
-1specific surface area.
Embodiment 7:
1) weighing 0.04mol purity is respectively the NiCl of 98.0%
26H
2o and 0.08mol purity is 99.0%CoCl
26H
2o, described NiCl
26H
2o and CoCl
26H
2the ratio of O amount is 1:2.By described NiCl
26H
2o and CoCl
26H
2o, is jointly dissolved in 100ml deionized water, is mixed with containing Ni
2+and Co
2+mixed salt solution A100ml, in described mixed salt solution A, Ni
2+and Co
2+total concn is 1.2mol/L.
2) by 0.18mol purity be 99.0% ammonium oxalate be dissolved in the mixed solvent of 50ml organic reagent ethanol and 50ml deionized water, described organic reagent to be purity be 99.7% ethanol, be configured to oxalate solution B.
3) 100ml mixed salt solution A step 1 configured is added drop-wise in the oxalate solution B that 100ml step 2 configures, and dropping limit, limit is stirred, and control temperature of reaction is 65 DEG C simultaneously, use aqueous ammonia conditions pH value, keep pH value to be 8.2, dropwise and continue stirring 0.5 hour, obtain precursor solution;
4) by step 3) the described precursor solution that obtains filters, and with deionized water wash four times, with absolute ethanol washing twice, obtained presoma, is placed on vacuum drying oven dry 24 hours by this presoma;
5) by step 4) presoma of obtained drying is placed in the electric furnace that PID regulates, and control temperature is 350 DEG C, carries out thermolysis in air atmosphere 1 hour, obtains mesoporous NiCo
2o
4fiber.
By step 5) the mesoporous cobalt acid nickel fiber that obtains characterizes, the bright synthesis of XRD figure stave be the sour nickel of cobalt, purity is high, does not have impurity.Tested from nitrogen adsorption-desorption isothermal curve, the mesoporous cobalt acid nickel fiber of synthesis has 55.8g
-1specific surface area.
Other physicochemical property of embodiment 1,2-7 product is as follows: minor axis≤250nm, fiber major diameter >=10 μm, carbon≤0.01wt%, sulphur≤0.001wt%, iron≤0.01wt%.
Above embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various modification that the common engineering technical personnel in this area make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (4)
1. a preparation method for mesoporous cobalt acid nickel fiber, is characterized in that, be made up of following steps:
1) soluble nickel salt and solubility cobaltates are dissolved in deionized water, are mixed with containing Ni
2+/ Co
2+mol ratio is the mixed salt solution A of 1:2;
2) be dissolved in by oxalate stoichiometrically in the mixed solvent of organic reagent and deionized water, be formulated as oxalate solution B, described organic reagent is the ethanol that purity is greater than 99.0%;
3) by step 1) the mixed salt solution A for preparing joins step 2) in the oxalate solution B for preparing, control temperature of reaction is 50 ~ 75 DEG C simultaneously, be 7.5 ~ 8.6 by ammoniacal liquor adjust ph, dropwise and continue stirring 0 ~ 2 hour, obtain precursor solution;
Wherein, in described oxalate solution B, described oxalate is oxalic acid or ammonium oxalate, and the concentration of oxalate is 0.3mol/L ~ 1.8mol/L, the Ni in oxalate and described mixed salt solution A
2+and Co
2+the ratio of total amount of substance be 1:1.0 ~ 1.5;
In described precursor solution, the volume ratio of organic reagent and deionized water is 1:1 ~ 20;
4) by step 3) precursor solution that obtains filters, with deionized water and absolute ethanol washing, the presoma after washing is dry;
5) by step 4) under obtained dried presoma is placed in 250 ~ 400 DEG C of temperature, carry out thermolysis 0.5 ~ 5 hour in air atmosphere.
2. preparation method according to claim 1, is characterized in that, in described precursor solution, the volume ratio of organic reagent and deionized water is 1:1 ~ 9.
3. preparation method according to claim 1, is characterized in that, described soluble nickel salt is selected from the one in nickelous chloride, single nickel salt, nickelous nitrate; Described soluble cobalt is selected from the one in cobalt chloride, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES.
4. preparation method according to claim 1, is characterized in that, in described mixed salt solution A, and Ni
2+and Co
2+total concn be 0.3mol/L ~ 1.2mol/L.
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| CN104003455B (en) * | 2014-06-18 | 2015-06-10 | 中国环境科学研究院 | Method for preparing multi-shape controllable nano nikel-cobalt spinel oxide |
| CN104291385B (en) * | 2014-08-26 | 2016-05-25 | 江苏合志锂硫电池技术有限公司 | Cobalt acid nickel mesoporous microsphere and preparation method thereof |
| CN106531448A (en) * | 2015-09-15 | 2017-03-22 | 上海杉杉科技有限公司 | Active carbon/nickel cobaltate nano wire composite electrode material and preparation method thereof |
| CN105470002A (en) * | 2015-11-27 | 2016-04-06 | 渤海大学 | Preparation method of nickel cobaltite porous micron belt/foamed nickel composite electrode material |
| CN105742070B (en) * | 2016-03-07 | 2017-12-05 | 深圳大学 | A kind of high catalytic activity solar cell is to electrode material and preparation method thereof |
| CN107419128B (en) * | 2017-06-22 | 2019-03-12 | 北京航空航天大学 | Using the method for three-dimensional communication nano porous metal preparation electrolysis water cathode hydrogen evolution electrode |
| CN111041508A (en) * | 2018-10-12 | 2020-04-21 | 丰田自动车株式会社 | Cobaltosic oxide array/titanium mesh water decomposition oxygen generation electrode and preparation method thereof |
| CN109772334A (en) * | 2018-12-28 | 2019-05-21 | 宁夏大学 | A kind of big mesoporous nickel cobalt glucose-sensitive material of high-specific surface area and preparation method thereof |
| CN111653789B (en) * | 2020-06-17 | 2022-05-27 | 泰州市海创新能源研究院有限公司 | Zinc-air battery catalyst and preparation method thereof |
| CN112058267A (en) * | 2020-09-18 | 2020-12-11 | 合肥工业大学 | Oxygen vacancy modified porous nickel-cobalt oxide nanobelt material and preparation method and application thereof |
| CN113617358B (en) * | 2021-09-14 | 2023-11-10 | 润和催化剂股份有限公司 | Preparation method of methanation catalyst |
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